CN114083853A - Light power cable reinforced protective sleeve and preparation method thereof - Google Patents

Light power cable reinforced protective sleeve and preparation method thereof Download PDF

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Publication number
CN114083853A
CN114083853A CN202111338170.7A CN202111338170A CN114083853A CN 114083853 A CN114083853 A CN 114083853A CN 202111338170 A CN202111338170 A CN 202111338170A CN 114083853 A CN114083853 A CN 114083853A
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flame
reinforced
preparation
retardant
power cable
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张龙
杨庆兵
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Jiangsu Guanzhixing Pipeline System Co ltd
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Jiangsu Guanzhixing Pipeline System Co ltd
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    • C08L23/04—Homopolymers or copolymers of ethene
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    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
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    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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Abstract

The invention provides a light power cable reinforced protective sleeve and a preparation method thereof, wherein the protective sleeve sequentially comprises a reinforced flame-retardant layer and an anti-corrosion layer from inside to outside, the reinforced flame-retardant layer is prepared by limiting raw materials and contents of components in the reinforced flame-retardant layer and using an ultraviolet irradiation crosslinking method, the crosslinking degree of the components in the reinforced flame-retardant layer is greatly improved, the light weight of the protective sleeve is realized, and the mechanical property of the reinforced flame-retardant layer is improved; in the reinforced flame-retardant layer, the flaky single-layer boron nitride is used as a modifier to modify polyethylene and light calcium carbonate, the used flame retardant is a DDP-dihydric alcohol polyphosphonate flame retardant, and a high-molecular antistatic agent is selected to form firm combination with other components in the reinforced flame-retardant layer under the action of ultraviolet light, so that a long-acting antistatic effect is achieved; the polyester fiber is modified in the corrosion-resistant layer through the modified multi-walled carbon nanotube, so that the wear resistance, the mechanical strength, the flame retardance and the corrosion resistance of the corrosion-resistant layer are greatly improved.

Description

Light power cable reinforced protective sleeve and preparation method thereof
Technical Field
The invention relates to the technical field of electric power facilities, in particular to a light power cable reinforced protective sleeve and a preparation method thereof.
Background
The power cable is a cable product for transmitting and distributing high-power electric energy, is mainly used in a trunk line of a power system, is commonly used for power stations, urban underground power grids, underwater power transmission lines and the like, and comprises various insulated power cables with various voltage grades of 1-500KV and above.
The use of power cables has been in the history of more than one hundred years, from the beginning of the development of underground transmission by the inventor in the united states in 1879 t.a. edison to the 80 s, ultra-high voltage power cables of 1200 kv have been made. The rapid growth of China economy provides a huge market space for cables, the cable industry is the second largest industry in China next to the automobile industry, and the domestic market share and the product variety satisfaction rate are both higher than 90%; with the continuous expansion of industries such as China data communication industry, power industry, urban rail transit industry, automobile industry and the like, the demand for wires and cables also increases rapidly; the requirements on the cable are continuously improved, and the cable has higher standard on the basic performance flame retardance and has high strength and high toughness.
The insulating sheath tube of the power cable is called sheath tube, and the sheath tube should also match the requirements of the cable, but the performance of the current sheath tube needs to be further improved.
Disclosure of Invention
The invention aims to provide a light power cable reinforced protective sleeve and a preparation method thereof, and aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the light power cable reinforced sheath pipe sequentially comprises a reinforced flame-retardant layer and a corrosion-resistant layer from inside to outside, wherein the reinforced flame-retardant layer comprises the following components in parts by weight: 45-50 parts of polyethylene, 37-42 parts of modifier, 12-15 parts of light calcium carbonate, 8-10 parts of antistatic agent, 8-10 parts of flame retardant and 2-8 parts of photosensitizer.
Further, the modifier is flaky single-layer hexagonal boron nitride.
Further, the preparation method of the modifier comprises the following steps: mixing and stirring borax, melamine, sodium dodecyl sulfate and deionized water, transferring the mixture into a microwave reactor, reacting for 20min at 100 ℃ under the microwave power of 550W, cooling in ice-water bath, centrifuging, and performing vacuum freeze drying to obtain a boron nitride precursor; and under the nitrogen atmosphere, heating the boron nitride precursor to 980 ℃ for reacting for 3h, cooling, washing the product with hot purified water, and drying to obtain the lamellar boron nitride.
The ratio of the amounts of boric acid and melamine species was 3: 1.
The hexagonal boron nitride has a graphite-like lamellar structure, large specific surface area, good self-lubricating property, excellent chemical inertness and gas barrier property, and the size of the commercially available powdery hexagonal boron nitride is usually in the range of hundreds of nanometers to tens of micrometers, is easy to agglomerate in a system and is difficult to disperse;
the boron nitride synthesized by the dual-temperature segmentation process is flaky particles with good crystal development, and the particle size range is 200-300 nm; the boron nitride synthesized by adopting ice-water bath cooling, microwave reaction and freeze drying is in a fiber-shaped form with a smooth surface, the toughness of the protective sleeve is improved by adding the modifier, the flame retardant property of the flame retardant layer can be further enhanced in a synergistic manner on the basis that the flame retardant agent improves the flame retardance of the polymer, and the flame retardant effect is increased by the overlapping and covering effect of the formed sheet layer boron nitride due to the addition of the sheet layer boron nitride; and the boron nitride has a morphological structure similar to that of carbon, and the addition of the boron nitride has the effect of a carbon forming agent, so that a carbon layer is formed after forming, and the flame retardance of the protective sleeve is greatly improved.
Further, the flame retardant is DDP-diol polyphosphonate flame retardant.
DDP is [ 6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] butanedioic acid; BOD is butanediol.
At present, organic flame retardants used in the market are mainly halogen flame retardants and phosphorus flame retardants, but the halogen flame retardants are not environment-friendly in the using process, can pollute the environment and do not meet the requirements of green production; however, most of phosphorus flame retardants are small-molecular phosphorus flame retardants, and the problems of easy migration and precipitation, large addition amount and the like exist when the phosphorus flame retardants are blended and modified with polyethylene;
the flame retardant used in the application is a DDP-diol polyphosphonate flame retardant, and is prepared by modifying a high-carbon side chain type phosphorus flame retardant DDP into a polyphosphonate flame retardant, because the DDP has large steric hindrance and is difficult to prepare, the polyphosphonate flame retardant is prepared by esterification and polycondensation of butanediol and the DDP, and the steric hindrance effect of the DDP is slowly released, so that the polyphosphonate flame retardant which is good in compatibility with polyethylene, hydrolysis resistance and flame retardant effect is prepared.
The phosphorus flame retardant DDP with a high-carbon-formation type phosphaphenanthrene ring structure is copolymerized with butanediol to form a polyphosphonate flame retardant with an ester bond in a main chain, so that the compatibility and hydrolysis resistance of polyphosphonate and polyethylene are improved;
further, the preparation method of the flame retardant comprises the following steps:
under the protection of nitrogen, mixing and stirring BOD and DDP, carrying out esterification reaction, then adding ethylene glycol antimony, vacuumizing, carrying out polycondensation reaction for 6 hours, and stopping the polycondensation reaction until a viscous rotor of a system is not rotated to obtain a polyphosphonate flame retardant;
the mol ratio of BOD to DDP is 1.2-1.24; the amount of ethylene glycol antimony is 0.4% of the total mass of BDP and DDP;
DDP is a molecule with a phosphaphenanthrene ring large steric hindrance structure, high steric hindrance effect makes the DDP difficult to generate macromolecules with dihydric alcohol, butanediol is a fat chain without side groups, the number of methylene groups is large, a molecular chain is long, flexibility is large, the steric hindrance effect of the DDP can be better relieved, in the later stage of polycondensation, as the molecular weight is increased, the viscosity of the system is increased, the bonding long chains with higher flexibility are bonded to generate the DDP-BDO polyphosphonate flame retardant with high polymerization degree, and the esterification rate of DDP and butanediol is high in the esterification stage, the number of carboxyl and hydroxyl groups participating in the reaction is large, the reaction degree is large, the polymerization degree is increased along with the increase of the reaction degree, therefore, the mol ratio of BOD and DDP is limited to be 1.2-1.24, the quantity of the ethylene glycol antimony is 0.4 percent of the total mass of the BDP and the DDP, can reach higher polymerization degree, and greatly improve the stability and the flame retardance of the flame retardant in the protective sleeve.
Further, the antistatic agent is a high-molecular antistatic agent, and the preparation method of the antistatic agent comprises the following steps: ultrasonically stirring acrylic acid polyoxyethylene ether, epoxy chloropropane, sodium hydroxide, tetrabutylammonium bromide and ethanol, reacting for 5-6h at 60-80 ℃, filtering, distilling under reduced pressure, adding acetone and imidazole, reacting for 1-2h at 55 ℃, and evaporating a solvent to obtain epoxy acrylic acid polyoxyethylene; adding hydrogen-containing siloxane, reacting at 70-80 deg.C for 0.5-1h, adding chloroplatinic acid, stirring, adding microcrystalline wax, epoxy siloxane and catalyst, and reacting under nitrogen protection for 0.5-1h to obtain the polymer antistatic agent.
Further, the mass ratio of the acrylic acid polyoxyethylene ether to the epoxy chloropropane to the sodium hydroxide to the tetrabutyl ammonium bromide is 30:8:1: 0.2; the mass ratio of the acetone to the imidazole is 25: 1; the mass ratio of the hydrogen-containing siloxane to the chloroplatinic acid to the microcrystalline wax to the catalyst is 15:0.02:3: 0.02.
Insulation is a great characteristic of cable sheath pipes, however, static electricity is accumulated after extrusion and friction are easily caused in the using process and is not easy to eliminate, and the surface static electricity accumulation can bring huge danger;
imidazole is introduced into acrylic polyoxyethylene ether and then grafted on hydrogen-containing siloxane to obtain hydrophilic polyether silicone oil, and simultaneously the hydrophilic polyether silicone oil and microcrystalline wax grafted with polar groups are crosslinked under the action of a coupling agent to obtain a high-molecular durable antistatic agent of the polar groups and the hydrophilic groups, and the high-molecular durable antistatic agent forms chemical bonds in a flame-retardant layer under the action of ultraviolet light to form firm combination so as to form a long-acting antistatic effect;
further, the photosensitizer is prepared from benzophenone and triethanolamine according to the mass ratio of 2: 1.
Further, a preparation method of the light power cable reinforced sheath pipe is characterized by comprising the following steps:
s1: preparing a reinforced flame-retardant layer: putting polyethylene, a modifier, light calcium carbonate, an antistatic agent, a flame retardant and a photosensitizer into a mixing roll to obtain a photo-crosslinking ingredient; adopting ultraviolet rays as a radiation source, extruding and coating the photo-crosslinking ingredients on a die, and performing ultraviolet crosslinking to obtain a flame-retardant layer;
s2: preparing a corrosion-resistant layer: dipping polyester fiber in a mixed modified solution of gamma-aminopropyl triethoxysilane and ethanol to obtain coupling agent modified fiber; then drying the carbon nano tube in the dispersion liquid of the carboxylated multi-wall carbon nano tube to obtain the carbon nano tube modified fiber; adding polyethylene, a carboxylated multi-walled carbon nanotube and carbon nanotube modified fibers into a double-screw extruder, and coating the reinforced flame-retardant layer with extrusion molding to form a corrosion-resistant layer, thereby obtaining the light power cable reinforced sheath pipe.
Further, in step S1, the ultraviolet light source is a high-pressure mercury lamp, and the ultraviolet crosslinking temperature is 185-.
Further, the preparation method of the carboxylated multi-wall carbon nanotube comprises the following steps: adding the carbon nano tube into a mixed acid solution of sulfuric acid and nitric acid at 18-26 ℃, carrying out ultrasonic treatment for 8h, washing with deionized water until the filtrate is neutral, and drying to obtain the carboxylated multi-wall carbon nano tube.
The invention adopts irradiation crosslinking to prepare the flame-retardant layer, polyethylene generates free radicals, hydrogen atoms and secondary free radicals under the action of ultraviolet rays, and the crosslinking reaction is generated when the formed free radicals meet the secondary free radicals. The polymer can generate cracking reaction while generating crosslinking reaction; therefore, the ultraviolet light source and the irradiation temperature are limited, and the crosslinking degree of the flame-retardant layer is ensured by matching the components in the flame-retardant layer.
The carboxyl is introduced to the surface of the multi-wall carbon nano tube, so that the original excellent properties of the multi-wall carbon nano tube can be maintained, the polarity and the hydrophilicity of the surface of the multi-wall carbon nano tube can be improved, and the binding capacity of other components in the corrosion-resistant layer can be improved; firstly, modifying polyester fiber by using a coupling agent, so that the carboxylated multi-walled carbon nanotube is tightly coated on the surface of the fiber without agglomeration to obtain a high-toughness and high-strength corrosion-resistant layer; the introduction of the carboxylated multi-walled carbon nano-tube not only ensures that the carbon nano-tube is uniformly dispersed, but also increases the tortuosity of gas and water entering the corrosion-resistant layer, greatly improves the flame-retardant and antibacterial performances of the corrosion-resistant layer and prolongs the service life of the protective sleeve.
The invention has the beneficial effects that:
the invention provides a light power cable reinforced protective sleeve and a preparation method thereof, wherein the protective sleeve sequentially comprises a reinforced flame-retardant layer and an anti-corrosion layer from inside to outside, the reinforced flame-retardant layer is prepared by limiting raw materials and contents of components in the reinforced flame-retardant layer and using an ultraviolet irradiation crosslinking method, the crosslinking degree of the components in the reinforced flame-retardant layer is greatly improved, the light weight of the protective sleeve is realized, and the mechanical property of the reinforced flame-retardant layer is improved;
in the reinforced flame-retardant layer, the flaky single-layer boron nitride is used as a modifier to modify polyethylene and light calcium carbonate, the boron nitride is in a fibrous form with a smooth surface, the toughness of the sheath pipe is improved by adding the modifier, the flame retardant property of the flame-retardant layer can be further enhanced in a synergistic manner on the basis that the flame retardant improves the flame retardance of a polymer, and the flame retardant effect is improved by adding the flaky boron nitride, so that the overlapping and covering effect of the formed flaky boron nitride; the boron nitride has a morphological structure similar to that of carbon, and the addition of the boron nitride has the effect of a carbon forming agent, so that a carbon layer is formed after forming, and the flame retardance of the protective sleeve is greatly improved;
the flame retardant used in the application is a DDP-diol polyphosphonate flame retardant, high-carbon-formation side chain type phosphorus flame retardant DDP is modified into the polyphosphonate flame retardant, the polyphosphonate flame retardant is prepared by esterification and polycondensation of diol and DDP, the steric effect of the DDP is slowly released, the polyphosphonate flame retardant which is good in compatibility with polyethylene, hydrolysis resistance and flame retardant effect is prepared, and the problems that small molecular phosphorus flame retardants used in the prior art are easy to migrate and separate out, large in addition amount and the like when being blended and modified with polyethylene in the prior art are solved;
according to the invention, imidazole is introduced into acrylic polyoxyethylene ether and then grafted on hydrogen-containing siloxane, so that the obtained polyether silicone oil has hydrophilicity, and simultaneously, the microcrystalline wax grafted with polar groups is crosslinked under the action of a coupling agent, so that the macromolecular antistatic agent with the polar groups and the hydrophilic groups is obtained, and chemical bonds are generated with other components in the enhanced flame retardant layer under the action of ultraviolet light to form firm combination, so that the long-acting antistatic effect is achieved;
the multi-walled carbon nanotubes are uniformly distributed on the polyester fiber to form modified fiber by modifying the multi-walled carbon nanotubes in the corrosion-resistant layer, and then the modified fiber and the polyethylene are co-extruded, so that the wear resistance, the mechanical strength, the flame retardance and the corrosion resistance of the corrosion-resistant layer are greatly improved.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that if directional indications such as up, down, left, right, front, and back … … are involved in the embodiment of the present invention, the directional indications are only used to explain a specific posture, such as a relative positional relationship between components, a motion situation, and the like, and if the specific posture changes, the directional indications also change accordingly. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The technical solutions of the present invention are further described in detail with reference to specific examples, which should be understood that the following examples are only illustrative of the present invention and are not intended to limit the present invention.
Example 1
A light power cable reinforced protective sleeve sequentially comprises a reinforced flame-retardant layer and a corrosion-resistant layer from inside to outside,
a preparation method of a light power cable reinforced sheath pipe comprises the following steps:
s1: preparing a reinforced flame-retardant layer: putting polyethylene, a modifier, light calcium carbonate, an antistatic agent, a flame retardant and a photosensitizer into a mixing roll to obtain a photo-crosslinking ingredient; adopting ultraviolet rays as a radiation source, extruding and coating the photo-crosslinking ingredients on a die, and performing ultraviolet crosslinking to obtain a flame-retardant layer;
the ultraviolet light source is a high-pressure mercury lamp, and the ultraviolet crosslinking temperature is 185 ℃;
the reinforced flame-retardant layer comprises the following components in parts by weight: 45 parts of polyethylene, 37 parts of modifier, 12 parts of light calcium carbonate, 8 parts of antistatic agent, 8 parts of flame retardant and 2 parts of photosensitizer;
the modifier is flaky single-layer hexagonal boron nitride; the preparation method of the modifier comprises the following steps: mixing and stirring borax, melamine, sodium dodecyl sulfate and deionized water, transferring the mixture into a microwave reactor, reacting for 20min at 100 ℃ under the microwave power of 550W, cooling in ice water bath, centrifuging, and performing vacuum freeze drying to obtain a boron nitride precursor; under the nitrogen atmosphere, heating the boron nitride precursor to 980 ℃ for reacting for 3h, cooling, washing the product with hot purified water, and drying to obtain lamellar boron nitride; the ratio of the amounts of boric acid and melamine species is 3: 1;
the flame retardant is a DDP-dihydric alcohol polyphosphonate flame retardant;
the preparation method of the flame retardant comprises the following steps:
under the protection of nitrogen, mixing and stirring BOD and DDP, carrying out esterification reaction, then adding ethylene glycol antimony, vacuumizing, carrying out polycondensation reaction for 6 hours, and stopping the polycondensation reaction until a viscous rotor of a system is not rotated to obtain a polyphosphonate flame retardant; the mol ratio of BOD to DDP is 1.2; the amount of ethylene glycol antimony is 0.4% of the total mass of BDP and DDP;
the antistatic agent is a high-molecular antistatic agent, and the preparation method of the antistatic agent comprises the following steps: ultrasonically stirring acrylic acid polyoxyethylene ether, epoxy chloropropane, sodium hydroxide, tetrabutylammonium bromide and ethanol, reacting for 6 hours at 60 ℃, filtering, distilling under reduced pressure, adding acetone and imidazole, reacting for 1 hour at 55 ℃, and evaporating a solvent to obtain epoxy acrylic acid polyoxyethylene; adding hydrogen-containing siloxane to react for 1 hour at 70 ℃, then adding chloroplatinic acid, continuously stirring, adding microcrystalline wax, epoxy siloxane and a catalyst, and reacting for 0.5 hour under the protection of nitrogen to obtain a high-molecular antistatic agent;
the mass ratio of the acrylic acid polyoxyethylene ether to the epoxy chloropropane to the sodium hydroxide to the tetrabutylammonium bromide is 30:8:1: 0.2; the mass ratio of the acetone to the imidazole is 25: 1; the mass ratio of the hydrogen-containing siloxane to the chloroplatinic acid to the microcrystalline wax to the catalyst is 15:0.02:3: 0.02;
the photosensitizer is prepared from benzophenone and triethanolamine according to the mass ratio of 2: 1;
s2: preparing a corrosion-resistant layer: dipping polyester fiber in a mixed modified solution of gamma-aminopropyl triethoxysilane and ethanol to obtain coupling agent modified fiber; then drying the carbon nano tube in the dispersion liquid of the carboxylated multi-wall carbon nano tube to obtain the carbon nano tube modified fiber; adding polyethylene, a carboxylated multi-walled carbon nanotube and carbon nanotube modified fibers into a double-screw extruder, and coating the reinforced flame-retardant layer by extrusion molding to form a corrosion-resistant layer, thereby obtaining the reinforced sheath tube of the light power cable;
the preparation method of the carboxylated multi-wall carbon nanotube comprises the following steps: adding the carbon nano tube into a mixed acid solution of sulfuric acid and nitric acid at 18 ℃, carrying out ultrasonic treatment for 8h, washing with deionized water until the filtrate is neutral, and drying to obtain the carboxylated multi-wall carbon nano tube.
Example 2
A light power cable reinforced protective sleeve sequentially comprises a reinforced flame-retardant layer and a corrosion-resistant layer from inside to outside,
a preparation method of a light power cable reinforced sheath pipe comprises the following steps:
s1: preparing a reinforced flame-retardant layer: putting polyethylene, a modifier, light calcium carbonate, an antistatic agent, a flame retardant and a photosensitizer into a mixing roll to obtain a photo-crosslinking ingredient; adopting ultraviolet rays as a radiation source, extruding and coating the photo-crosslinking ingredients on a die, and performing ultraviolet crosslinking to obtain a flame-retardant layer;
the ultraviolet light source is a high-pressure mercury lamp, and the ultraviolet crosslinking temperature is 188 ℃;
the reinforced flame-retardant layer comprises the following components in parts by weight: 48 parts of polyethylene, 40 parts of modifier, 13 parts of light calcium carbonate, 9 parts of antistatic agent, 9 parts of flame retardant and 5 parts of photosensitizer;
the modifier is flaky single-layer hexagonal boron nitride; the preparation method of the modifier comprises the following steps: mixing and stirring borax, melamine, sodium dodecyl sulfate and deionized water, transferring the mixture into a microwave reactor, reacting for 20min at 100 ℃ under the microwave power of 550W, cooling in ice water bath, centrifuging, and performing vacuum freeze drying to obtain a boron nitride precursor; under the nitrogen atmosphere, heating the boron nitride precursor to 980 ℃ for reacting for 3h, cooling, washing the product with hot purified water, and drying to obtain lamellar boron nitride; the ratio of the amounts of boric acid and melamine species is 3: 1;
the flame retardant is a DDP-dihydric alcohol polyphosphonate flame retardant;
the preparation method of the flame retardant comprises the following steps:
under the protection of nitrogen, mixing and stirring BOD and DDP, carrying out esterification reaction, then adding ethylene glycol antimony, vacuumizing, carrying out polycondensation reaction for 6 hours, and stopping the polycondensation reaction until a viscous rotor of a system is not rotated to obtain a polyphosphonate flame retardant; the mol ratio of BOD to DDP is 1.23; the amount of ethylene glycol antimony is 0.4% of the total mass of BDP and DDP;
the antistatic agent is a high-molecular antistatic agent, and the preparation method of the antistatic agent comprises the following steps: ultrasonically stirring acrylic acid polyoxyethylene ether, epoxy chloropropane, sodium hydroxide, tetrabutylammonium bromide and ethanol, reacting for 5.5h at the temperature of 60-80 ℃, filtering, distilling under reduced pressure, adding acetone and imidazole, reacting for 1.5h at the temperature of 55 ℃, and evaporating a solvent to obtain epoxy acrylic acid polyoxyethylene; adding hydrogen-containing siloxane to react for 0.8h at 75 ℃, then adding chloroplatinic acid, continuously stirring, adding microcrystalline wax, epoxy siloxane and a catalyst, and reacting for 0.8h under the protection of nitrogen to obtain a high-molecular antistatic agent;
the mass ratio of the acrylic acid polyoxyethylene ether to the epoxy chloropropane to the sodium hydroxide to the tetrabutylammonium bromide is 30:8:1: 0.2; the mass ratio of the acetone to the imidazole is 25: 1; the mass ratio of the hydrogen-containing siloxane to the chloroplatinic acid to the microcrystalline wax to the catalyst is 15:0.02:3: 0.02;
the photosensitizer is prepared from benzophenone and triethanolamine according to the mass ratio of 2: 1;
s2: preparing a corrosion-resistant layer: dipping polyester fiber in a mixed modified solution of gamma-aminopropyl triethoxysilane and ethanol to obtain coupling agent modified fiber; then drying the carbon nano tube in the dispersion liquid of the carboxylated multi-wall carbon nano tube to obtain the carbon nano tube modified fiber; adding polyethylene, a carboxylated multi-walled carbon nanotube and carbon nanotube modified fibers into a double-screw extruder, and coating the reinforced flame-retardant layer by extrusion molding to form a corrosion-resistant layer, thereby obtaining the reinforced sheath tube of the light power cable;
the preparation method of the carboxylated multi-wall carbon nanotube comprises the following steps: adding the carbon nano tube into a mixed acid solution of sulfuric acid and nitric acid at 22 ℃, carrying out ultrasonic treatment for 8h, washing with deionized water until the filtrate is neutral, and drying to obtain the carboxylated multi-wall carbon nano tube.
Example 3
A light power cable reinforced protective sleeve sequentially comprises a reinforced flame-retardant layer and a corrosion-resistant layer from inside to outside,
a preparation method of a light power cable reinforced sheath pipe comprises the following steps:
s1: preparing a reinforced flame-retardant layer: putting polyethylene, a modifier, light calcium carbonate, an antistatic agent, a flame retardant and a photosensitizer into a mixing roll to obtain a photo-crosslinking ingredient; adopting ultraviolet rays as a radiation source, extruding and coating the photo-crosslinking ingredients on a die, and performing ultraviolet crosslinking to obtain a flame-retardant layer;
the ultraviolet light source is a high-pressure mercury lamp, and the ultraviolet crosslinking temperature is 190 ℃;
the reinforced flame-retardant layer comprises the following components in parts by weight: 50 parts of polyethylene, 42 parts of modifier, 15 parts of light calcium carbonate, 10 parts of antistatic agent, 10 parts of flame retardant and 8 parts of photosensitizer;
the modifier is flaky single-layer hexagonal boron nitride; the preparation method of the modifier comprises the following steps: mixing and stirring borax, melamine, sodium dodecyl sulfate and deionized water, transferring the mixture into a microwave reactor, reacting for 20min at 100 ℃ under the microwave power of 550W, cooling in ice water bath, centrifuging, and performing vacuum freeze drying to obtain a boron nitride precursor; under the nitrogen atmosphere, heating the boron nitride precursor to 980 ℃ for reacting for 3h, cooling, washing the product with hot purified water, and drying to obtain lamellar boron nitride; the ratio of the amounts of boric acid and melamine species is 3: 1;
the flame retardant is a DDP-dihydric alcohol polyphosphonate flame retardant;
the preparation method of the flame retardant comprises the following steps:
under the protection of nitrogen, mixing and stirring BOD and DDP, carrying out esterification reaction, then adding ethylene glycol antimony, vacuumizing, carrying out polycondensation reaction for 6 hours, and stopping the polycondensation reaction until a viscous rotor of a system is not rotated to obtain a polyphosphonate flame retardant; the mol ratio of BOD to DDP is 1.24; the amount of ethylene glycol antimony is 0.4% of the total mass of BDP and DDP;
the antistatic agent is a high-molecular antistatic agent, and the preparation method of the antistatic agent comprises the following steps: ultrasonically stirring acrylic acid polyoxyethylene ether, epoxy chloropropane, sodium hydroxide, tetrabutylammonium bromide and ethanol, reacting for 5 hours at 80 ℃, filtering, distilling under reduced pressure, adding acetone and imidazole, reacting for 1 hour at 55 ℃, and evaporating a solvent to obtain epoxy acrylic acid polyoxyethylene; adding hydrogen-containing siloxane to react for 0.5h at 80 ℃, then adding chloroplatinic acid, continuously stirring, adding microcrystalline wax, epoxy siloxane and a catalyst, and reacting for 1h under the protection of nitrogen to obtain a high-molecular antistatic agent;
the mass ratio of the acrylic acid polyoxyethylene ether to the epoxy chloropropane to the sodium hydroxide to the tetrabutylammonium bromide is 30:8:1: 0.2; the mass ratio of the acetone to the imidazole is 25: 1; the mass ratio of the hydrogen-containing siloxane to the chloroplatinic acid to the microcrystalline wax to the catalyst is 15:0.02:3: 0.02;
the photosensitizer is prepared from benzophenone and triethanolamine according to the mass ratio of 2: 1;
s2: preparing a corrosion-resistant layer: dipping polyester fiber in a mixed modified solution of gamma-aminopropyl triethoxysilane and ethanol to obtain coupling agent modified fiber; then drying the carbon nano tube in the dispersion liquid of the carboxylated multi-wall carbon nano tube to obtain the carbon nano tube modified fiber; adding polyethylene, a carboxylated multi-walled carbon nanotube and carbon nanotube modified fibers into a double-screw extruder, and coating the reinforced flame-retardant layer by extrusion molding to form a corrosion-resistant layer, thereby obtaining the reinforced sheath tube of the light power cable;
the preparation method of the carboxylated multi-wall carbon nanotube comprises the following steps: adding the carbon nano tube into a mixed acid solution of sulfuric acid and nitric acid at 26 ℃, carrying out ultrasonic treatment for 8h, washing with deionized water until the filtrate is neutral, and drying to obtain the carboxylated multi-wall carbon nano tube.
Comparative example 1
A light power cable reinforced protective sleeve sequentially comprises a reinforced flame-retardant layer and a corrosion-resistant layer from inside to outside,
a preparation method of a light power cable reinforced sheath pipe comprises the following steps:
s1: preparing a reinforced flame-retardant layer: putting polyethylene, light calcium carbonate, an antistatic agent, a flame retardant and a photosensitizer into a mixing roll to obtain a photo-crosslinking ingredient; adopting ultraviolet rays as a radiation source, extruding and coating the photo-crosslinking ingredients on a die, and performing ultraviolet crosslinking to obtain a flame-retardant layer;
the ultraviolet light source is a high-pressure mercury lamp, and the ultraviolet crosslinking temperature is 188 ℃;
the reinforced flame-retardant layer comprises the following components in parts by weight: 48 parts of polyethylene, 13 parts of light calcium carbonate, 9 parts of antistatic agent, 9 parts of flame retardant and 5 parts of photosensitizer;
the flame retardant is a DDP-dihydric alcohol polyphosphonate flame retardant;
the preparation method of the flame retardant comprises the following steps:
under the protection of nitrogen, mixing and stirring BOD and DDP, carrying out esterification reaction, then adding ethylene glycol antimony, vacuumizing, carrying out polycondensation reaction for 6 hours, and stopping the polycondensation reaction until a viscous rotor of a system is not rotated to obtain a polyphosphonate flame retardant; the mol ratio of BOD to DDP is 1.23; the amount of ethylene glycol antimony is 0.4% of the total mass of BDP and DDP;
the antistatic agent is a high-molecular antistatic agent, and the preparation method of the antistatic agent comprises the following steps: ultrasonically stirring acrylic acid polyoxyethylene ether, epoxy chloropropane, sodium hydroxide, tetrabutylammonium bromide and ethanol, reacting for 5.5h at the temperature of 60-80 ℃, filtering, distilling under reduced pressure, adding acetone and imidazole, reacting for 1.5h at the temperature of 55 ℃, and evaporating a solvent to obtain epoxy acrylic acid polyoxyethylene; adding hydrogen-containing siloxane to react for 0.8h at 75 ℃, then adding chloroplatinic acid, continuously stirring, adding microcrystalline wax, epoxy siloxane and a catalyst, and reacting for 0.8h under the protection of nitrogen to obtain a high-molecular antistatic agent;
the mass ratio of the acrylic acid polyoxyethylene ether to the epoxy chloropropane to the sodium hydroxide to the tetrabutylammonium bromide is 30:8:1: 0.2; the mass ratio of the acetone to the imidazole is 25: 1; the mass ratio of the hydrogen-containing siloxane to the chloroplatinic acid to the microcrystalline wax to the catalyst is 15:0.02:3: 0.02;
the photosensitizer is prepared from benzophenone and triethanolamine according to the mass ratio of 2: 1;
s2: preparing a corrosion-resistant layer: dipping polyester fiber in a mixed modified solution of gamma-aminopropyl triethoxysilane and ethanol to obtain coupling agent modified fiber; then drying the carbon nano tube in the dispersion liquid of the carboxylated multi-wall carbon nano tube to obtain the carbon nano tube modified fiber; adding polyethylene, a carboxylated multi-walled carbon nanotube and carbon nanotube modified fibers into a double-screw extruder, and coating the reinforced flame-retardant layer by extrusion molding to form a corrosion-resistant layer, thereby obtaining the reinforced sheath tube of the light power cable;
the preparation method of the carboxylated multi-wall carbon nanotube comprises the following steps: adding the carbon nano tube into a mixed acid solution of sulfuric acid and nitric acid at 22 ℃, carrying out ultrasonic treatment for 8h, washing with deionized water until the filtrate is neutral, and drying to obtain the carboxylated multi-wall carbon nano tube.
Comparative example 2
A light power cable reinforced protective sleeve sequentially comprises a reinforced flame-retardant layer and a corrosion-resistant layer from inside to outside,
a preparation method of a light power cable reinforced sheath pipe comprises the following steps:
s1: preparing a reinforced flame-retardant layer: putting polyethylene, a modifier, light calcium carbonate, an antistatic agent, a flame retardant and a photosensitizer into a mixing roll to obtain a photo-crosslinking ingredient; adopting ultraviolet rays as a radiation source, extruding and coating the photo-crosslinking ingredients on a die, and performing ultraviolet crosslinking to obtain a flame-retardant layer;
the ultraviolet light source is a high-pressure mercury lamp, and the ultraviolet crosslinking temperature is 188 ℃;
the reinforced flame-retardant layer comprises the following components in parts by weight: 48 parts of polyethylene, 40 parts of modifier, 13 parts of light calcium carbonate, 9 parts of antistatic agent, 9 parts of flame retardant and 5 parts of photosensitizer;
the modifier is flaky single-layer hexagonal boron nitride; the preparation method of the modifier comprises the following steps: mixing and stirring borax, melamine, sodium dodecyl sulfate and deionized water, transferring the mixture into a microwave reactor, reacting for 20min at 100 ℃ under the microwave power of 550W, cooling in ice water bath, centrifuging, and performing vacuum freeze drying to obtain a boron nitride precursor; under the nitrogen atmosphere, heating the boron nitride precursor to 980 ℃ for reacting for 3h, cooling, washing the product with hot purified water, and drying to obtain lamellar boron nitride; the ratio of the amounts of boric acid and melamine species is 3: 1;
the flame retardant is a micromolecular phosphate ester flame retardant;
the antistatic agent is a high-molecular antistatic agent, and the preparation method of the antistatic agent comprises the following steps: ultrasonically stirring acrylic acid polyoxyethylene ether, epoxy chloropropane, sodium hydroxide, tetrabutylammonium bromide and ethanol, reacting for 5.5h at the temperature of 60-80 ℃, filtering, distilling under reduced pressure, adding acetone and imidazole, reacting for 1.5h at the temperature of 55 ℃, and evaporating a solvent to obtain epoxy acrylic acid polyoxyethylene; adding hydrogen-containing siloxane to react for 0.8h at 75 ℃, then adding chloroplatinic acid, continuously stirring, adding microcrystalline wax, epoxy siloxane and a catalyst, and reacting for 0.8h under the protection of nitrogen to obtain a high-molecular antistatic agent;
the mass ratio of the acrylic acid polyoxyethylene ether to the epoxy chloropropane to the sodium hydroxide to the tetrabutylammonium bromide is 30:8:1: 0.2; the mass ratio of the acetone to the imidazole is 25: 1; the mass ratio of the hydrogen-containing siloxane to the chloroplatinic acid to the microcrystalline wax to the catalyst is 15:0.02:3: 0.02;
the photosensitizer is prepared from benzophenone and triethanolamine according to the mass ratio of 2: 1;
s2: preparing a corrosion-resistant layer: dipping polyester fiber in a mixed modified solution of gamma-aminopropyl triethoxysilane and ethanol to obtain coupling agent modified fiber; then drying the carbon nano tube in the dispersion liquid of the carboxylated multi-wall carbon nano tube to obtain the carbon nano tube modified fiber; adding polyethylene, a carboxylated multi-walled carbon nanotube and carbon nanotube modified fibers into a double-screw extruder, and coating the reinforced flame-retardant layer by extrusion molding to form a corrosion-resistant layer, thereby obtaining the reinforced sheath tube of the light power cable;
the preparation method of the carboxylated multi-wall carbon nanotube comprises the following steps: adding the carbon nano tube into a mixed acid solution of sulfuric acid and nitric acid at 22 ℃, carrying out ultrasonic treatment for 8h, washing with deionized water until the filtrate is neutral, and drying to obtain the carboxylated multi-wall carbon nano tube.
Comparative example 3
A light power cable reinforced protective sleeve sequentially comprises a reinforced flame-retardant layer and a corrosion-resistant layer from inside to outside,
a preparation method of a light power cable reinforced sheath pipe comprises the following steps:
s1: preparing a reinforced flame-retardant layer: putting polyethylene, a modifier, light calcium carbonate, an antistatic agent, a flame retardant and a photosensitizer into a mixing roll to obtain a photo-crosslinking ingredient; adopting ultraviolet rays as a radiation source, extruding and coating the photo-crosslinking ingredients on a die, and performing ultraviolet crosslinking to obtain a flame-retardant layer;
the ultraviolet light source is a high-pressure mercury lamp, and the ultraviolet crosslinking temperature is 188 ℃;
the reinforced flame-retardant layer comprises the following components in parts by weight: 48 parts of polyethylene, 40 parts of modifier, 13 parts of light calcium carbonate, 9 parts of antistatic agent, 9 parts of flame retardant and 5 parts of photosensitizer;
the modifier is flaky single-layer hexagonal boron nitride; the preparation method of the modifier comprises the following steps: mixing and stirring borax, melamine, sodium dodecyl sulfate and deionized water, transferring the mixture into a microwave reactor, reacting for 20min at 100 ℃ under the microwave power of 550W, cooling in ice water bath, centrifuging, and performing vacuum freeze drying to obtain a boron nitride precursor; under the nitrogen atmosphere, heating the boron nitride precursor to 980 ℃ for reacting for 3h, cooling, washing the product with hot purified water, and drying to obtain lamellar boron nitride; the ratio of the amounts of boric acid and melamine species is 3: 1;
the flame retardant is a DDP-dihydric alcohol polyphosphonate flame retardant;
the preparation method of the flame retardant comprises the following steps:
under the protection of nitrogen, mixing and stirring BOD and DDP, carrying out esterification reaction, then adding ethylene glycol antimony, vacuumizing, carrying out polycondensation reaction for 6 hours, and stopping the polycondensation reaction until a viscous rotor of a system is not rotated to obtain a polyphosphonate flame retardant; the mol ratio of BOD to DDP is 1.23; the amount of ethylene glycol antimony is 0.4% of the total mass of BDP and DDP;
the antistatic agent is carbon black;
the mass ratio of the acrylic acid polyoxyethylene ether to the epoxy chloropropane to the sodium hydroxide to the tetrabutylammonium bromide is 30:8:1: 0.2; the mass ratio of the acetone to the imidazole is 25: 1; the mass ratio of the hydrogen-containing siloxane to the chloroplatinic acid to the microcrystalline wax to the catalyst is 15:0.02:3: 0.02;
the photosensitizer is prepared from benzophenone and triethanolamine according to the mass ratio of 2: 1;
s2: preparing a corrosion-resistant layer: dipping polyester fiber in a mixed modified solution of gamma-aminopropyl triethoxysilane and ethanol to obtain coupling agent modified fiber; then drying the carbon nano tube in the dispersion liquid of the carboxylated multi-wall carbon nano tube to obtain the carbon nano tube modified fiber; adding polyethylene, a carboxylated multi-walled carbon nanotube and carbon nanotube modified fibers into a double-screw extruder, and coating the reinforced flame-retardant layer by extrusion molding to form a corrosion-resistant layer, thereby obtaining the reinforced sheath tube of the light power cable;
the preparation method of the carboxylated multi-wall carbon nanotube comprises the following steps: adding the carbon nano tube into a mixed acid solution of sulfuric acid and nitric acid at 22 ℃, carrying out ultrasonic treatment for 8h, washing with deionized water until the filtrate is neutral, and drying to obtain the carboxylated multi-wall carbon nano tube.
Comparative example 4
A light power cable reinforced protective sleeve sequentially comprises a reinforced flame-retardant layer and a corrosion-resistant layer from inside to outside,
a preparation method of a light power cable reinforced sheath pipe comprises the following steps:
s1: preparing a reinforced flame-retardant layer: putting polyethylene, light calcium carbonate, an antistatic agent, a flame retardant and a photosensitizer into a mixing roll to obtain a photo-crosslinking ingredient; adopting ultraviolet rays as a radiation source, extruding and coating the photo-crosslinking ingredients on a die, and performing ultraviolet crosslinking to obtain a flame-retardant layer;
the ultraviolet light source is a high-pressure mercury lamp, and the ultraviolet crosslinking temperature is 188 ℃;
the reinforced flame-retardant layer comprises the following components in parts by weight: 48 parts of polyethylene, 40 parts of modifier, 13 parts of light calcium carbonate, 9 parts of antistatic agent, 9 parts of flame retardant and 5 parts of photosensitizer;
the flame retardant is a micromolecular phosphate ester flame retardant;
the antistatic agent is carbon black;
the photosensitizer is prepared from benzophenone and triethanolamine according to the mass ratio of 2: 1;
s2: preparing a corrosion-resistant layer: dipping polyester fiber in a mixed modified solution of gamma-aminopropyl triethoxysilane and ethanol to obtain coupling agent modified fiber; and (3) co-extruding and compounding the modified fiber and the polyethylene on the reinforced flame-retardant layer to form the corrosion-resistant layer, so as to obtain the light power cable reinforced sheath pipe.
And (3) performance testing: the sheath pipes obtained in examples 1 to 3 and comparative examples 1 to 4 were subjected to a performance test: testing the oxygen index by reference to GB/T2406-2009; measuring the volume resistivity at 25 ℃ by referring to GB-T15738-; testing the tensile strength and the elongation at break of the obtained sheath tube by referring to GB/T1040-2018; referring to the flame retardant grade of the sheath pipe obtained by the vertical combustion test in GB/T2408-2008;
and (3) testing salt resistance: placing the protective sleeve obtained in the embodiment 1-3 into 2g/L sodium chloride solution to be soaked for 10 days to observe the surface condition; the measurement results are shown in Table 1;
Figure BDA0003351238960000131
Figure BDA0003351238960000141
TABLE 1
Examples 1-3 were prepared according to the process of the present invention, comparative example 1 was prepared without the addition of a modifier; the flame retardant in comparative example 2 is a small molecule phosphate ester flame retardant; comparative example 3 is where the antistatic agent is carbon black; comparative example 4 is no modifier added, the flame retardant is a small molecule phosphate ester flame retardant, and the antistatic agent is carbon black; as can be seen from the comparison between example 2 and comparative examples 1 to 4, the sheath pipe prepared by the method has excellent mechanical properties, excellent flame retardance and corrosion resistance, and the service life of the sheath pipe is greatly prolonged.
The above description is only an example of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (10)

1. The preparation method of the light power cable reinforced sheath pipe is characterized by comprising the following steps:
s1: preparing a reinforced flame-retardant layer: putting polyethylene, a modifier, light calcium carbonate, an antistatic agent, a flame retardant and a photosensitizer into a mixing roll to obtain a photo-crosslinking ingredient; adopting ultraviolet rays as a radiation source, extruding and coating the photo-crosslinking ingredients on a die, and performing ultraviolet crosslinking to obtain a reinforced flame-retardant layer;
s2: preparing a corrosion-resistant layer: dipping polyester fiber in a mixed modified solution of gamma-aminopropyl triethoxysilane and ethanol to obtain coupling agent modified fiber; then drying the carbon nano tube in the dispersion liquid of the carboxylated multi-wall carbon nano tube to obtain the carbon nano tube modified fiber; adding polyethylene, a carboxylated multi-walled carbon nanotube and carbon nanotube modified fibers into a double-screw extruder, and coating the reinforced flame-retardant layer with extrusion molding to form a corrosion-resistant layer, thereby obtaining the light power cable reinforced sheath pipe.
2. The preparation method of the light power cable reinforced sheath pipe as claimed in claim 1, wherein the reinforced flame-retardant layer comprises the following components in parts by weight: 45-50 parts of polyethylene, 37-42 parts of modifier, 12-15 parts of light calcium carbonate, 8-10 parts of antistatic agent, 8-10 parts of flame retardant and 2-8 parts of photosensitizer.
3. The preparation method of the lightweight power cable reinforcing sheath pipe as claimed in claim 1, wherein the modifier is lamellar single-layer hexagonal boron nitride.
4. The method for preparing the reinforced sheath tube of the light power cable according to claim 1, wherein the flame retardant is DDP-diol polyphosphonate flame retardant.
5. The preparation method of the lightweight power cable reinforcing sheath pipe as claimed in claim 4, wherein the preparation method of the flame retardant comprises the following steps: under the protection of nitrogen, mixing and stirring butanediol and DDP, carrying out esterification reaction, then adding ethylene glycol antimony, vacuumizing, carrying out polycondensation reaction for 6 hours, and stopping the polycondensation reaction until a viscous rotor of a system is not rotated to obtain the polyphosphonate flame retardant.
6. The preparation method of the light-weight power cable reinforcing sheath pipe as claimed in claim 1, wherein the preparation method of the antistatic agent comprises the following steps: ultrasonically stirring acrylic acid polyoxyethylene ether, epoxy chloropropane, sodium hydroxide, tetrabutylammonium bromide and ethanol, reacting for 5-6h at 60-80 ℃, filtering, distilling under reduced pressure, adding acetone and imidazole, reacting for 1-2h at 55 ℃, and evaporating a solvent to obtain epoxy acrylic acid polyoxyethylene; adding hydrogen-containing siloxane to react for 0.5-1h at 70-80 ℃, then adding chloroplatinic acid, continuing stirring, adding microcrystalline wax, epoxy siloxane and a catalyst, and reacting for 0.5-1h under the protection of nitrogen to obtain the antistatic agent.
7. The preparation method of the light power cable reinforcing sheath pipe of claim 6, wherein the mass ratio of the acrylic acid polyoxyethylene ether, the epichlorohydrin, the sodium hydroxide and the tetrabutylammonium bromide is 30:8:1: 0.2; the mass ratio of the acetone to the imidazole is 25: 1; the mass ratio of the hydrogen-containing siloxane to the chloroplatinic acid to the microcrystalline wax to the catalyst is 15:0.02:3: 0.02.
8. The method for preparing the reinforced sheath tube of the light power cable according to claim 1, wherein the photosensitizer is benzophenone and triethanolamine according to a mass ratio of 2: 1.
9. The method as claimed in claim 1, wherein the UV source in step S1 is a high pressure mercury lamp, and the UV crosslinking temperature is 185-190 ℃.
10. The preparation method of the lightweight power cable reinforcing sheath tube according to claim 1, wherein the preparation method of the carboxylated multi-walled carbon nanotube comprises the following steps: adding the carbon nano tube into a mixed acid solution of sulfuric acid and nitric acid at 18-26 ℃, carrying out ultrasonic treatment for 8h, washing with deionized water until the filtrate is neutral, and drying to obtain the carboxylated multi-wall carbon nano tube.
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CN114805984B (en) * 2022-04-25 2023-02-17 广东中讯通讯设备实业有限公司 High-heat-dissipation HDPE electric power conduit and preparation method thereof

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